New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate Is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 degrees C with Pt-CeO(2) catalyst and at 50 degrees C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis from zinc oxalate, growth mechanism and optical properties of ZnO nano/micro structures

We report the synthesis of various morphological micro to nano structured zinc oxide crystals via simple precipitation technique. The growth mechanisms of the zinc oxide nanostructures such as snowflake, rose, platelets, porous pyramid and rectangular shapes were studied in detail under various growth conditions. The precursor powders were prepared using several zinc counter ions such as chloride, nitrate and sulphate along with oxalic acid as a precipitating agent. The precursors were decomposed by heating in air resulting in the formation of different shapes of zinc oxide crystals. Variations in ZnO nanostructural shapes were possibly due to the counter ion effect. Sulphate counter ion led to unusual rose-shape morphology. Strong ultrasonic treatment on ZnO rose shows that it was formed by irregular arrangement of micro to nano size hexagonal zinc oxide platelets. The X-ray diffraction studies confirmed the wurzite structure of all zinc oxide samples synthesized using different zinc counter ions. Functional groups of the zinc oxalate precursor and zinc oxide were identified using micro Raman studies. The blue light emission spectra of the various morphologies were recorded using luminescence spectrometer. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Mechanism of enhanced corrosion of alumina graphite refractories near slag/metal interface

All refractories show enhanced corrosion near the slag/metal interface due to Marangoni and convective flows. However, in the case of oxide refractories containing graphite flakes, corrosion is severe due to periodic oscillations in the contact angle at the slag/metal interface, resulting in cyclic dissolution of oxide and graphite into the slag and metal, respectively. Alumina--graphite (AG) refractories should be used only where they are not in simultaneous contact with slag (flux) and low carbon steel.

Tribology of ethylene-air diffusion flame soot under dry and lubricated contact conditions

Soot particles are generated in a flame caused by burning ethylene gas. The particles are collected thermophoretically at different locations of the flame. The particles are used to lubricate a steel/steel ball on flat reciprocating sliding contact, as a dry solid lubricant and also as suspended in hexadecane. Reciprocating contact is shown to establish a protective and low friction tribo-film. The friction correlates with the level of graphitic order of the soot, which is highest in the soot extracted from the mid-flame region and is low in the soot extracted from the flame root and flame tip regions. Micro-Raman spectroscopy of the tribo-film shows that the a priori graphitic order, the molecular carbon content of the soot and the graphitization of the film as brought about by tribology distinguish between the frictions of soot extracted from different regions of the flame, and differentiate the friction associated with dry tribology from that recorded under lubricated tribology.

Photocatalytic Activity of Combustion Synthesized ZrO(2) and ZrO(2)-TiO(2) Mixed Oxides

Tetragonal ZrO(2), synthesized by solution combustion technique, was found to be photocatalytically active for the degradation of anionic dyes. The compound was characterized by FT-Raman spectroscopy, X-ray photoelectron spectroscopy, FT-infrared spectroscopy, UV-vis spectroscopy, BET surface area analysis, and zero point charge pH measurement. A high concentration of surface hydroxyl groups was observed over the catalyst, as confirmed by XPS and FUR. The photocatalytic degradation of orange G, amido black, remazol brilliant blue R, and alizarin cyanine green (ACG) was carried out with this material. The effect of pH, inorganic. salts, and H(2)O(2) on the activity of the catalyst was also studied, and it was found that the catalyst maintained its activity at a wide range of pH and in the presence of inorganic salts. Having established that ZrO(2) was photocatalytically active, mixed oxide catalysts of TiO(2)-ZrO(2) were also tested for the photocatalytic degradation of ACG, and the 50% ZrO(2)-TiO(2) mixed oxides showed activity that was comparable to the activity of TiO(2).

A Mechanism for the Occurrence of Ions in Distilled Water

Solar distillation can be used to produce potable water from contaminated water. However, studies show that ions such as F(-) and NO(3)(-) occur in distillates from solar stills. In order to understand the reasons for this behavior, imaging and distillation experiments were conducted. White dots were seen in the vapor space above the interface of hot water poured into containers. The concentrations of various ions such as F(-) and SO(4)(2-) in the distillates from thermal and solar distillation experiments were roughly comparable when the feed consisted of deionized water and also solutions having fluoride concentrations of 100 and 10 000 mg/L. These observations suggest that aerosols enter the distillation setup through leaks and provide nuclei for the condensation of water vapor. The water-soluble component of aerosols dissolves in the drops formed, and some of the drops are transferred to the distillate by buoyancy-driven convection.

Effect of Adiabatic Flame Temperature on Nano Alumina Powders during Solution Combustion Process

Nano ceramic alumina powders are synthesized by solution combustion synthesis using aluminium nitrate as oxidizer and urea as fuel with different fuel to oxidizer ratio. The variation of adiabatic flame temperatures are calculated theoretically for different fuel/oxidizer ratio according to thermodynamic concept and correlated with the observed flame (reaction) temperatures. A ``multi channel thermocouple setup connected to computer interfaced Keithley multi meter 2700'' is used to monitor the thermal events occurring during the process. The combustion products, characterized by XRD, show that the powders are composed of polycrystalline oxides with crystallite size of 32 to 52 nm. An interpretation based on maximum combustion temperature and the amount of gases produced during reaction for various fuel to oxide ratio has been proposed for the nature of combustion and its correlation with the characteristics of as-synthesized powder.

A compliant mechanism kit with flexible beams and connectors along with analysis and optimal synthesis procedures

We present a compliant mechanism kit as a parallel to the kits available for rigid-body mechanisms. The kit consists of flexible beams and connectors that can be easily hand-assembled using snap fits. The mechanisms assembled using the kit accurately capture the aspects of the topology, shape, and size of joint-free compliant mechanisms. Thus, the kit enables designers to conceive and design new, practicable, single-piece compliant mechanisms that do not require assembly. The concept of the kit also resolves a discrepancy in the finite element (FE) modeling of beam-based compliant mechanisms. The discrepancy arises when two or more beams are joined at one point and thus leading to increased stiffness. After resolving this discrepancy, this work extends the topology optimization to automatically generate designs that can be assembled with the kit for quick and easy validation instead of time-consuming prototyping. Thus, the kit and the accompanying analysis and optimal synthesis procedures comprise a self-contained educational as well as a research and practice toolset for compliant mechanisms. The paper also illustrates how human creativity finds new ways of using the kit beyond the original intended use and how it enables even a novice to design compliant mechanisms. (C) 2011 Elsevier Ltd. All rights reserved.